WO2014114721A1 - Dérivés de 4-n-aminopipéridine (disubstituée) comme additifs pour des masses de moulage de polyamide et leur utilisation - Google Patents

Dérivés de 4-n-aminopipéridine (disubstituée) comme additifs pour des masses de moulage de polyamide et leur utilisation Download PDF

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Publication number
WO2014114721A1
WO2014114721A1 PCT/EP2014/051343 EP2014051343W WO2014114721A1 WO 2014114721 A1 WO2014114721 A1 WO 2014114721A1 EP 2014051343 W EP2014051343 W EP 2014051343W WO 2014114721 A1 WO2014114721 A1 WO 2014114721A1
Authority
WO
WIPO (PCT)
Prior art keywords
independently
alkyl
additive
alcohol
polyamide molding
Prior art date
Application number
PCT/EP2014/051343
Other languages
German (de)
English (en)
Inventor
Johannes Katzer
Original Assignee
Uhde Inventa-Fischer Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Uhde Inventa-Fischer Gmbh filed Critical Uhde Inventa-Fischer Gmbh
Priority to CN201480006196.3A priority Critical patent/CN105143184B/zh
Priority to EA201591060A priority patent/EA029652B1/ru
Priority to US14/763,086 priority patent/US9908973B2/en
Priority to KR1020157019718A priority patent/KR20150125645A/ko
Priority to JP2015554146A priority patent/JP6496249B2/ja
Publication of WO2014114721A1 publication Critical patent/WO2014114721A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/56—Nitrogen atoms
    • C07D211/58—Nitrogen atoms attached in position 4

Definitions

  • the invention relates to an additive having at least two condensable functionalities in combination with a Tetraalkyi-piperidinyl radical and a tertiary amine functionality.
  • a universal additive can be provided, which on the one hand allows a narrower molecular weight distribution and at the same time improves the performance for spun polymers.
  • likewise corresponding additized polyamide molding compositions and an additive solution are provided.
  • the additives according to the invention are used in particular in the production of polyamide for textile applications.
  • the threads must be well dyeable.
  • Additives to achieve the desired performance must be available and applicable at an economic cost-benefit ratio.
  • the use of multifunctional stabilizers has proven to have a narrowing effect on the molecular weight distribution.
  • multifunctional carboxylic acids are used which at the same time keep the content of primary amine groups in the condensation equilibrium low and are thus favorable for a low monomer recovery during remelting.
  • Examples of the use of multifunctional acids as additives for the production of polyamides are EP 0 818 491 A1 and EP 0 759 953 Al mentioned.
  • the narrowing influence on the molecular weight distribution is e.g. the article by Z.-L Tang et al.
  • Chain length regulator acting, but the molecular weight distribution non-modifying compounds possible, such. with said 4-amino-2,2,6,6-tetramethylpiperidine.
  • it is important to minimize the number of reactive chain ends. This reduces the rate of postcondensation and monomer recovery, e.g. when remelting polyamide 6.
  • the quantitative use of chain length controllers is limited by the process engineering possibilities and the consideration of economic factors.
  • amino end groups are important for good staining, such as e.g. described in EP 0 818 491 AI, tertiary amines introduced into the polymer. These can not undergo amide bond and therefore remain for the
  • R 1 independently of one another are H or C 1 -C 2 -alkyl
  • R 2 H or CC 12 alkyl
  • X and Y independently represent an aliphatic or unsaturated or aromatic carbon skeleton, linear or branched, having 1 to 12 carbon atoms, wherein X and Y each have at least one carboxy, an amine or an alcohol functionality.
  • the additive according to the invention provides for a narrower molecular weight distribution compared to a partial or complete stabilization with monofunctional chain length regulators.
  • the HALS compound as well as the tertiary amine are not bound to the chain end as usual, but are incorporated into the chain and, assuming the same process conditions, no longer reduce the potential for lowering the polydispersity. A performance gain in the field of high-speed spinning is therefore expected.
  • the additive according to the invention makes it possible for the first time to be able to serve the stated requirements for textile polyamide with a single compound. This reduces dosing distances and storage tanks to a minimum and at the same time reduces the number of suppliers on which production depends.
  • the structures are based on existing mass Chemicals can be produced and there are no additional costs to existing, comparable multi-component formulations expected.
  • the structures mentioned make it possible for the first time to incorporate the HALS compound or the tertiary amine into the polymer chain. So far, only binding to the chain end is possible via quasi-monofunctional compounds, which limits the possibilities of modifying the molecular weight distribution. By gaining the potential to make the molecular weight distribution narrower, increases in performance in the area of high-speed spinning are possible because the melt strength is reduced, but the strength increases in the solidified state.
  • a preferred additive according to the invention has the general formula II:
  • R 1 and R 2 are each independently H or C 1 -C 2 -alkyl
  • R 3 is independently H or an aliphatic or unsaturated or aromatic carbon skeleton, linear or branched, having 1 to 12 carbon atoms and
  • n are each independently 0 to 10.
  • At least one of R 3 has a carboxy functionality.
  • at least one of R 3 is CH 2 COOH.
  • an additive solution which contains the above-described additive together with caprolactam.
  • Other additives may be included in this solution.
  • the additive solution may additionally contain bifunctional carboxylic acids, such as terephthalic acid and / or adipic acid.
  • bifunctional carboxylic acids such as terephthalic acid and / or adipic acid.
  • a polyamide molding composition which has an additive, wherein the additive is covalently bound via at least two condensable functionalities in the polymer chain.
  • units of general formula IV are incorporated into the polymer chain:
  • Ri and 2 are each independently H or Ci- Ci2 alkyl
  • R 3 is independently H or an aliphatic or unsaturated or aromatic carbon skeleton, linear or branched, having 1 to 12 carbon atoms and
  • S and T are independently 0, NH or COO and
  • n are each independently 0 to 10.
  • R 2 are each independently H or CC i2 alkyl
  • R 3 is independently H or an aliphatic or unsaturated or aromatic carbon skeleton, iinear or branched, having 1 to 12 carbon atoms and
  • n are each independently 0 to 10.
  • the polyamide molding compound has a polydispersity in the range in the range of 1.3 to 2.5, in particular 1.5 to 2.0.
  • the additive according to the invention is used in the production of polycondensates, in particular of
  • Caprolactam is polymerized at a constant water content of 300 mmol / kg (0.54 w%) at 245 ° C until the polycondensation equilibrium is reached. Subsequently, the polymer is granulated and hot
  • Caprolactam and 41.7 mmol / kg of acetic acid are polymerized at a constant water content of 125 mmol / kg (0.225 w%) at 245 ° C until reaching the Poikkondensations Dermatheses.
  • the further processing is analogous to Comparative Example 1.
  • Triacetonediamine be at a constant water content of
  • Caprolactam, 19.03 mmol / kg terephthalic acid and 17.5 mmol / kg compound II I are polymerized at a constant water content of 125 mmol / kg (0.225 w-%) at 245 ° C until the polycondensation equilibrium is reached.
  • the further processing is analogous to Comparative Example 1.
  • Table 1 compares the properties of the synthesized polymers of Comparative Beisptele 1 to 3 and Example 1 of the invention. All have the same relative viscosity, which can be used as a measure of processability in the molten state.
  • Table 1 compares the properties of the synthesized polymers of Comparative Beisptele 1 to 3 and Example 1 of the invention. All have the same relative viscosity, which can be used as a measure of processability in the molten state.

Abstract

L'invention concerne un additif comportant au moins deux fonctionnalités condensables en combinaison avec un radical tétra-alkyle-pipéridinyl ainsi qu'une fonctionnalité amine tertiaire. Par la combinaison de ces fonctionnalités, on peut réaliser un additif universel qui, d'une part, permet une répartition plus étroite des masses molaires et qui améliore en même temps les performances pour des polymères filés. Selon l'invention, on fournit de même des masses de moulage à additifs, ainsi qu'une solution de l'additif. Les additifs selon l'invention trouvent en particulier des applications lors de la production du polyamide pour des applications textiles.
PCT/EP2014/051343 2013-01-25 2014-01-23 Dérivés de 4-n-aminopipéridine (disubstituée) comme additifs pour des masses de moulage de polyamide et leur utilisation WO2014114721A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201480006196.3A CN105143184B (zh) 2013-01-25 2014-01-23 作为用于聚酰胺模塑化合物的添加剂的4‑n‑(二取代)‑氨基哌啶衍生物及其用途
EA201591060A EA029652B1 (ru) 2013-01-25 2014-01-23 Добавка к полиамидным формовочным массам и ее применение
US14/763,086 US9908973B2 (en) 2013-01-25 2014-01-23 Additive for polyamide moulding compounds and use thereof
KR1020157019718A KR20150125645A (ko) 2013-01-25 2014-01-23 폴리아미드 성형 재료용 첨가제로서의 4-n-(이치환된)-아미노피페리딘 유도체 및 이의 용도
JP2015554146A JP6496249B2 (ja) 2013-01-25 2014-01-23 ポリアミドモールディングコンパウンド用添加剤およびその使用

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP13152696.4 2013-01-25
EP13152696.4A EP2759534B1 (fr) 2013-01-25 2013-01-25 Derivés de 4-N-(disubstitués)-aminopipéridine comme additifs pour masses de formage en polyamide et leur utilisation

Publications (1)

Publication Number Publication Date
WO2014114721A1 true WO2014114721A1 (fr) 2014-07-31

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2014/051343 WO2014114721A1 (fr) 2013-01-25 2014-01-23 Dérivés de 4-n-aminopipéridine (disubstituée) comme additifs pour des masses de moulage de polyamide et leur utilisation

Country Status (10)

Country Link
US (1) US9908973B2 (fr)
EP (1) EP2759534B1 (fr)
JP (1) JP6496249B2 (fr)
KR (1) KR20150125645A (fr)
CN (1) CN105143184B (fr)
EA (1) EA029652B1 (fr)
ES (1) ES2538802T3 (fr)
PL (1) PL2759534T3 (fr)
TW (1) TWI602877B (fr)
WO (1) WO2014114721A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023242597A1 (fr) 2022-06-16 2023-12-21 Amphista Therapeutics Limited Molécules bifonctionnelles pour la dégradation ciblée de protéines
WO2024057021A1 (fr) 2022-09-13 2024-03-21 Amphista Therapeutics Limited Composés pour la dégradation ciblée d'une protéine

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DE2719132A1 (de) * 1976-05-11 1977-12-01 Ciba Geigy Ag Modifizierte polyurethane mit erhoehter lichtbestaendigkeit
US4145512A (en) * 1976-09-21 1979-03-20 Bayer Aktiengesellschaft Permanently stabilized polyurethanes
EP0047967A1 (fr) * 1980-09-10 1982-03-24 The B.F. GOODRICH Company Dérivés de pipéridine à haut poids moléculaire, utilisables comme stabilisants
EP0488502A1 (fr) * 1990-11-29 1992-06-03 Texaco Chemical Company Tert-amino-4 tétraalkyl-2,2,6,6 pipéridines
WO1997005189A1 (fr) * 1995-07-27 1997-02-13 Alliedsignal Inc. Substrat polyamide photostabilise et procede de fabrication
EP0759953A1 (fr) 1994-04-15 1997-03-05 Basf Aktiengesellschaft Polyamides intrinsequement stables a la lumiere et a la chaleur
EP0818491A2 (fr) 1996-07-09 1998-01-14 Ems-Inventa Ag Polaymides résistant aux imtempéries et leur méthode de préparation
EP0839854A1 (fr) * 1996-05-16 1998-05-06 Toray Industries, Inc. Film polyester etire bi-axialement et destine au moulage de contenants et procede de fabrication associe
DE19804980A1 (de) * 1998-02-07 1999-08-12 Huels Chemische Werke Ag Hydroxyl- und uretdiongruppenhaltige Polyisocyanate mit eingebautem HALS-Stabilisator, ein Verfahren zu ihrer Herstellung und deren Verwendung
DE19812135A1 (de) * 1998-03-20 1999-09-23 Basf Ag Inhärent licht- und hitzestabilisierte Polyamide mit verbesserter Naßechtheit
DE19854421A1 (de) 1998-11-25 2000-05-31 Inventa Ag Verfahren zur Herstellung von Polyamid-6 für Spinnzwecke
US20020169181A1 (en) * 2001-03-08 2002-11-14 Michel Pairet Pharmaceutical compositions based on anticholinergics and NK1-receptor antagonists
DE102008026075A1 (de) 2008-05-30 2009-12-03 Lurgi Zimmer Gmbh Verfahren zur Herstellung von Polyamiden unter Verwendung von Carbonsäuren und Amiden

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DE2545647C3 (de) * 1975-10-11 1982-03-11 Bayer Ag, 5090 Leverkusen Stabilisierung synthetischer Polymerer
DE2642374A1 (de) * 1976-09-21 1978-03-23 Bayer Ag Permanent stabilisierte polyurethane
US4348524A (en) * 1980-03-28 1982-09-07 Ciba-Geigy Corporation Amide derivatives of polyalkylpiperidines
CA1266272A (fr) * 1983-05-27 1990-02-27 Masakatsu Yoshimura Derive de 2,2,6,6-tetramethylpiperidine; methode de preparation; stabilisateur a base de ce derive pour les resines synthetiques
JPS59219346A (ja) 1983-05-27 1984-12-10 Sumitomo Chem Co Ltd 合成樹脂用安定剤
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US4145512A (en) * 1976-09-21 1979-03-20 Bayer Aktiengesellschaft Permanently stabilized polyurethanes
EP0047967A1 (fr) * 1980-09-10 1982-03-24 The B.F. GOODRICH Company Dérivés de pipéridine à haut poids moléculaire, utilisables comme stabilisants
EP0488502A1 (fr) * 1990-11-29 1992-06-03 Texaco Chemical Company Tert-amino-4 tétraalkyl-2,2,6,6 pipéridines
EP0759953A1 (fr) 1994-04-15 1997-03-05 Basf Aktiengesellschaft Polyamides intrinsequement stables a la lumiere et a la chaleur
WO1997005189A1 (fr) * 1995-07-27 1997-02-13 Alliedsignal Inc. Substrat polyamide photostabilise et procede de fabrication
EP0839854A1 (fr) * 1996-05-16 1998-05-06 Toray Industries, Inc. Film polyester etire bi-axialement et destine au moulage de contenants et procede de fabrication associe
EP0818491A2 (fr) 1996-07-09 1998-01-14 Ems-Inventa Ag Polaymides résistant aux imtempéries et leur méthode de préparation
DE19804980A1 (de) * 1998-02-07 1999-08-12 Huels Chemische Werke Ag Hydroxyl- und uretdiongruppenhaltige Polyisocyanate mit eingebautem HALS-Stabilisator, ein Verfahren zu ihrer Herstellung und deren Verwendung
DE19812135A1 (de) * 1998-03-20 1999-09-23 Basf Ag Inhärent licht- und hitzestabilisierte Polyamide mit verbesserter Naßechtheit
DE19854421A1 (de) 1998-11-25 2000-05-31 Inventa Ag Verfahren zur Herstellung von Polyamid-6 für Spinnzwecke
US20020169181A1 (en) * 2001-03-08 2002-11-14 Michel Pairet Pharmaceutical compositions based on anticholinergics and NK1-receptor antagonists
DE102008026075A1 (de) 2008-05-30 2009-12-03 Lurgi Zimmer Gmbh Verfahren zur Herstellung von Polyamiden unter Verwendung von Carbonsäuren und Amiden

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023242597A1 (fr) 2022-06-16 2023-12-21 Amphista Therapeutics Limited Molécules bifonctionnelles pour la dégradation ciblée de protéines
WO2024057021A1 (fr) 2022-09-13 2024-03-21 Amphista Therapeutics Limited Composés pour la dégradation ciblée d'une protéine

Also Published As

Publication number Publication date
CN105143184A (zh) 2015-12-09
EP2759534A1 (fr) 2014-07-30
JP2016511777A (ja) 2016-04-21
TW201439206A (zh) 2014-10-16
EP2759534B1 (fr) 2015-03-11
KR20150125645A (ko) 2015-11-09
CN105143184B (zh) 2017-10-03
US20150329671A1 (en) 2015-11-19
ES2538802T3 (es) 2015-06-24
PL2759534T3 (pl) 2015-08-31
JP6496249B2 (ja) 2019-04-03
EA029652B1 (ru) 2018-04-30
US9908973B2 (en) 2018-03-06
EA201591060A1 (ru) 2015-12-30
TWI602877B (zh) 2017-10-21

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